This invention pertains to certain thermally-stable, anthraquinone colorant compounds (dyes) which contain one or more vinyl groups which render the compounds copolymerizable with reactive vinyl monomers to produce colored, polymeric compositions such as acrylate and methacrylate polymeric materials. The compounds possess good fastness (stability) to ultraviolet (UV) light, good solubility in vinyl monomers, good color strength and excellent thermal stability. The present invention includes acrylic polymeric materials, i.e., polymers derived from acrylic acid esters, methacrylic acid esters and/or other copolymerizable vinyl compounds, having copolymerized therein one or more of the dye compounds of the present invention.
It is known (J.S.D.C., April 1977, pp 114-125) to produce colored polymeric materials by combining a reactive polymer such terepolymers having epoxy groups or polyacryloyl chloride with anthraquinone dyes containing nucleophilic reactive groups such as amino or hydroxy groups; to graft acryloylaminoanthraquinone dyes to the backbone of vinyl or divinyl polymers; and to polymerize anthraquinone dyes containing certain olefinic groups to produce polymeric dyes/pigments. U.S. Pat. No. 4,115,056 describes the preparation of blue, substituted 1,4-diaminoanthraquinone dyes containing one acryloyloxy group and and the use of the dyes in coloring various fibers, especially polyamide fibers. U.S. Pat. No. 4,943,617 discloses liquid crystalline copolymers containing certain blue, substituted 1,5-diamino-4,8-dihydroxyanthraquinone dyes containing an olefinic group copolymerized therein to provide liquid crystal copolymers having high dichromism. U.S. Pat. No. 5,055,602 describes the preparation of certain substituted 1,4-diaminoanthraquinone dyes containing polymerizable acryloyl and methacryloyl groups and their use in coloring polyacrylate contact lens materials by copolymerizing.
U.S. Pat. No. 5,362,812 discloses the conversion of a variety of dye classes, including anthraquinones, into polymeric dyes by (a) polymerizing 2-alkenylazlactones and reacting the polymer with dyes containing nucleophilic groups and by (b) reacting a nucleophilic dye with an alkenylazlactone and then polymerizing the free radically polymerizable dyes thus produced. The polymeric dyes are reported to be useful for photoresist systems and for colorproofing. U.S. Pat. No. 5,367,039 discloses a process for preparing colored vinyl polymers suitable for inks, paints, toners and the like by emulsion polymerization of a vinyl monomer with reactive anthraquinone dyes prepared by functionalizing certain anthraquinone dyes with methacryloyl groups.
The preparation of a variety of dyes, including some anthraquinones, which contain photopolymerizable groups and their use for color filters suitable for use in liquid crystal television sets, color copying machines, photosensitive resist resin compositions, and the like are described in U.S. Pat. No. 5,578,419.
One embodiment of the present invention concerns anthraquinone dye or colorant compounds represented by general Formulae I-XXI set forth below. The dyes having Formulae I-VII are blue-cyan colorants, the dyes having Formulae VIII-XVIII are red-magenta colorants, and the dyes having Formulae XIX-XXI are yellow colorants. 
wherein:
R is selected from hydrogen or 1-3 groups selected from C1-C6-alkyl, C1-C6-alkoxy and halogen;
R1 is selected from C1-C6-alkyl, substituted C1-C6-alkyl, C3-C8-alkenyl, C3-C8-cycloalkyl, aryl and xe2x80x94L1xe2x80x94Zxe2x80x94Q; R2=selected from hydrogen, C1-C6-alkyl, substituted C1-C6-alkyl, C3-C8-cycloalkyl and aryl;
R3 and R4 are independently selected from C1-C6-alkyl and bromine;
R5 is selected from C1-C6-alkyl, substituted C1-C6 alkyl, C3-C8-cycloalkyl, aryl, heteroaryl, xe2x80x94L1xe2x80x94Zxe2x80x94Q, 
R6 is selected from 
R7 is selected from hydrogen, substituted or unsubstituted C1-C6-alkyl, C1-C6-alkoxy, halogen, hydroxy, substituted or unsubstituted C1-C6-alkylthio, sulfamoyl and substituted sulfamoyl;
R8 is selected from hydrogen and C1-C6-alkyl;
R9 is selected from the groups represented by R1 and xe2x80x94Lxe2x80x94Zxe2x80x94Q;
R10 is selected from hydrogen and halogen;
X is a covalent bond or a divalent linking group selected from xe2x80x94Oxe2x80x94, xe2x80x94Sxe2x80x94, xe2x80x94SO2xe2x80x94, xe2x80x94CO2xe2x80x94, xe2x80x94CON(Y)xe2x80x94 and xe2x80x94SO2N(Y)xe2x80x94, wherein Y is selected from hydrogen, C1-C6-alkyl, substituted C1-C6-alkyl, C3-C8-cycloalkyl, C3-C8-alkenyl, aryl and xe2x80x94Lxe2x80x94Zxe2x80x94Q;
X1 is selected from xe2x80x94Oxe2x80x94, xe2x80x94Sxe2x80x94, xe2x80x94SO2xe2x80x94 and xe2x80x94SO2N(Y)xe2x80x94;
X2 is selected from xe2x80x94CO2xe2x80x94 and xe2x80x94SO2N(Y1), wherein Y1 is a group selected from hydrogen, C1-C6-alkyl, substituted C1-C6-alkyl, C3-C8-alkenyl, C3-C8-cycloalkyl, aryl heteroaryl and xe2x80x94CH2-p-C6H4xe2x80x94C(R8)xe2x95x90CH2;
X3 is selected from xe2x80x94CO2xe2x80x94, xe2x80x94SO2N(Y)xe2x80x94;
X4 is selected from xe2x80x94CO2xe2x80x94, xe2x80x94Oxe2x80x94 and xe2x80x94SO2N(Y1)xe2x80x94;
L is a divalent linking group selected from C1-C8-alkylene, C1-C6-alkylene-arylene, arylene, C1-C6-alkylene-arylene-C1-C6-alkylene, C3-C8-cycloalkylene, C1-C6-alkylene-C3-C8-cycloalkylene-C1-C6-alkylene, C1-C6-alkylene-Z1-arylene-Z1-C1-C6-alkylene and C2-C6-alkylene-[-Z1-C2-C6-alkylene-]n- wherein Z1 is selected from xe2x80x94Oxe2x80x94, xe2x80x94Sxe2x80x94 and xe2x80x94SO2, and n is 1-3;
L1 is a divalent linking group selected from C2-C6-alkylene, C1-C6-alkylene-C3-C8-cycloalkylene-C1-C6-alkylene, C1-C6-alkylene-arylene, C3-C8-cycloalkylene, and C2-C6-alkylene-[-Z1-C2-C6-alkylene-]n-;
L2 is selected from C2-C6-alkylene, C1-C6-alkylene-arylene-C1-C6 alkylene and C1-C6-alkylene-C3-C8-cycloalkylene-C1-C6-alkylene;
Z is a divalent group selected from xe2x80x94Oxe2x80x94, xe2x80x94Sxe2x80x94, xe2x80x94NHxe2x80x94, xe2x80x94N(C1-C6-alkyl)-, xe2x80x94N(C3-C8 alkenyl)-, xe2x80x94N(C3-C8 cycloalkyl)-, xe2x80x94N(aryl)-, xe2x80x94N(SO2C1-C6-alkyl) and xe2x80x94N(SO2 aryl)-, provided that when Q is a photopolymerizable optionally substituted maleimide radical, Z represents a covalent bond; Q is an ethylenically-unsaturated, photosensitive polymerizable group; and
m and m1 each is 0 or 1.
xe2x80x94CONHxe2x80x94C1-C6-alkylene OCOC(R11)xe2x80x94CHxe2x95x90CHxe2x80x94R12xe2x80x83xe2x80x83IIIa
xe2x80x94CONHxe2x80x94C1-C6-alkylene OCOC(R11)xe2x80x94CHxe2x95x90CHxe2x80x94R12xe2x80x83xe2x80x83IIIa
The ethylenically-unsaturated, photosensitive copolymerizable groups represented by Q are selected from the following organic radicals: 
wherein:
R11 is selected from hydrogen and C1-C6-alkyl;
R12 is selected from hydrogen; C1-C6-alkyl; phenyl and phenyl substituted with one or more groups selected from C1-C6-alkyl, C1-C6-alkoxy, xe2x80x94N(C1-C6-alkyl), nitro, cyano, C1-C6-alkoxycarbonyl, C1-C6-alkanoyloxy and halogen; 1- and 2-naphthyl which may be substituted with C1-C6-alkyl or C1-C6-alkoxy; 2- and 3-thienyl which may be substituted with C1-C6-alkyl or halogen; 2- or 3-furyl which may be substituted with C1-C6-alkyl;
R13 and R14 are selected from hydrogen, C1-C6-alkyl, substituted C1-C6-alkyl, aryl or may be combined to represent a xe2x80x94[xe2x80x94CH2xe2x80x94]3-5xe2x80x94 radical;
R15 is selected from hydrogen, C1-C6-alkyl, substituted C1-C6-alkyl, C3-C8-alkenyl, C3-C8-cycloalkyl and aryl;
R16 is selected from hydrogen, C1-C6-alkyl and aryl.
The term xe2x80x9cC1-C6-alkylxe2x80x9d is used herein to denote a straight or branched chain, saturated, aliphatic hydrocarbon radical containing one to six carbon atoms. The term xe2x80x9csubstituted C1-C6-alkylxe2x80x9d is used to denote a C1-C6-alkyl group substituted with one or more groups, preferably one to three groups, selected from the group consisting of hydroxy, halogen, cyano, aryl, aryloxy, arylthio, C1-C6 alkylthio, C3-C8-cycloalkyl, C1-C6-alkanoyloxy and xe2x80x94[xe2x80x94Oxe2x80x94R17xe2x80x94)xe2x80x94R18, wherein R17 is selected from the group consisting of C1-C6 alkylene, C1-C6-alkylene-arylene, cyclohexylene, arylene, C1-C6-alkylene-cyclohexylene and C1-C6-alkylene-cyclohexylene-C1-C6-alkylene;
R18 is selected from the group consisting of hydrogen, hydroxy, carboxy, C1-C6-alkanoyloxy, C2-C6-alkoxycarbonyl, aryl and C3-C8-cycloalkyl; and p is 1, 2, or 3.
A second embodiment of the present invention pertains to a coating composition comprising (i) one or more polymerizable vinyl compounds, (ii) one or more of the dye compounds described above, and (iii) a photoinitiator. A third embodiment of the present invention pertains to a polymeric composition, typically a coating, comprising a polymer of one or more acrylic acid esters, one or more methacrylic acid esters and/or other polymerizable vinyl compounds, having copolymerized therein one or more of the dye compounds described above.